JP6012983B2 - Coated powder and method for producing the same - Google Patents
Coated powder and method for producing the same Download PDFInfo
- Publication number
- JP6012983B2 JP6012983B2 JP2012041680A JP2012041680A JP6012983B2 JP 6012983 B2 JP6012983 B2 JP 6012983B2 JP 2012041680 A JP2012041680 A JP 2012041680A JP 2012041680 A JP2012041680 A JP 2012041680A JP 6012983 B2 JP6012983 B2 JP 6012983B2
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- Prior art keywords
- powder
- coating
- heat
- acid
- organic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
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- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- DCWZELMIUJYGMS-UHFFFAOYSA-N tetradecyl 2,2-dimethylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)(C)C DCWZELMIUJYGMS-UHFFFAOYSA-N 0.000 description 1
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
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- 239000010497 wheat germ oil Substances 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
- Glanulating (AREA)
Description
本発明は、被覆粉体及びその製造方法に関する。また、本発明は、前記の被覆粉体を含む分散体、化粧料に関する。 The present invention relates to a coated powder and a method for producing the same. Moreover, this invention relates to the dispersion and cosmetics containing the said coating powder.
粉体の表面に有機化合物を被覆すると、粉体の分散性、貯蔵安定性、使用適性を高めたり、粉体の機能、例えば、皮膚への付着力(付着性)、感触(使用感)、光沢、隠蔽力、着色力、透明性、紫外線や赤外線の遮蔽能、導電性、蛍光性、発光性、触媒活性等を飛躍的に向上させたりすることができる。このため、有機化合物を被覆した粉体は、化粧料、プラスチックの添加剤、インク、塗料、トナー(磁性粉、外添剤)、化学繊維、包装材料、電子材料等の各種分野で広く使用されている。 When the surface of the powder is coated with an organic compound, the dispersibility, storage stability and suitability for use of the powder are improved, and the function of the powder, for example, adhesion to the skin (adhesion), feel (use feeling), Gloss, hiding power, coloring power, transparency, shielding ability of ultraviolet rays and infrared rays, conductivity, fluorescence, luminescence, catalytic activity, etc. can be greatly improved. For this reason, powders coated with organic compounds are widely used in various fields such as cosmetics, plastic additives, inks, paints, toners (magnetic powders, external additives), chemical fibers, packaging materials, and electronic materials. ing.
このような有機化合物被覆粉体は例えば、特許文献1には、粉体にジメチコン(ジメチルポリシロキサン)とジメチコン/メチコンコポリマー(メチルハイドロジェンシロキサン−ジメチルシロキサン共重合体)との混合物をミキサーで混合して、粉体の表面に前記混合物を被覆することを記載している。 For example, Patent Document 1 discloses such an organic compound-coated powder in which a mixture of dimethicone (dimethylpolysiloxane) and dimethicone / methicone copolymer (methylhydrogensiloxane-dimethylsiloxane copolymer) is mixed with a powder using a mixer. Then, it is described that the mixture is coated on the surface of the powder.
また、特許文献2には、粉体の粒子表面に形成された反応性オルガノポリシロキサン等の常温で固体状の表面処理剤被覆層(A層)及び片末端官能基変性オルガノポリシロキサン等の常温で液体状の表面処理剤被覆層(B層)とを含有する表面処理粉体であって、ヘンシルミキサーやスーパーミキサー等で処理すべき粉体と固体状の表面処理剤を混合した後、液体状の表面処理剤を混合し乾燥する乾式法、JETミルのような高速気流中で処理すべき粉体と固体状の表面処理剤を接触させ被覆した後更に、液体状の表面処理剤を接触させて被覆する方法等を記載している。 Patent Document 2 discloses a normal surface treatment agent coating layer (A layer) such as a reactive organopolysiloxane formed on the particle surface of a powder at room temperature and a normal temperature such as one-end functional group-modified organopolysiloxane. In the surface treatment powder containing the liquid surface treatment agent coating layer (B layer), after mixing the powder to be treated with a Hensyl mixer or a super mixer and the solid surface treatment agent, A dry method in which a liquid surface treatment agent is mixed and dried, and after the powder to be treated and a solid surface treatment agent are contacted and coated in a high-speed air current such as a JET mill, a liquid surface treatment agent is further added. It describes the method of coating by contact.
特許文献1や2の方法で製造した有機化合物被覆粉体では、有機化合物の被覆によって油性分散性(疎水性)が得られているが、使用中に油性分散性が徐々に低下するため、長期間の分散安定性に優れた被覆粉体が求められている。
In the organic compound-coated powder produced by the methods of Patent Documents 1 and 2, oil-based dispersibility (hydrophobicity) is obtained by coating the organic compound, but the oil-based dispersibility gradually decreases during use. There is a need for coated powders that are excellent in dispersion stability over time.
そこで、本発明者らは、個々の粒子により強固な被覆を行えば、使用中に有機化合物の被覆が剥がれにくく、分散安定性を改善できると考えて種々研究した結果、粉体表面の少なくとも一部に形成された有機化合物の第一加熱固定被覆及びその被覆の上の少なくとも一部に有機化合物の第二加熱固定被覆を形成することにより、所望の被覆粉体が得られること、このような被覆粉体は、粉体と第一被覆有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理して第一加熱固定被覆を形成する工程と、前記の工程で得られた粉体と第二被覆有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理して第二加熱固定被覆を形成する工程を行うことにより製造できることなどを見出し、本発明を完成した。 Accordingly, the present inventors have conducted various studies on the assumption that if a strong coating is performed with individual particles, the coating of the organic compound is difficult to peel off during use and the dispersion stability can be improved. Forming a first heat-fixed coating of the organic compound formed on the part and a second heat-fixed coating of the organic compound on at least a part of the coating, thereby obtaining a desired coating powder, such as The coated powder includes a step in which the powder and the first coated organic compound are pulverized in an airflow pulverizer, followed by heat treatment to form a first heat fixed coating, and the powder obtained in the above step and the first The present invention was completed by finding that it can be produced by carrying out a step of forming a second heat-fixed coating by heat treatment and pulverizing the two-coated organic compound in an airflow pulverizer.
すなわち、本発明は、(1)粉体表面の少なくとも一部に形成された有機化合物の第一加熱固定被覆及びその第一加熱固定被覆の上の少なくとも一部に形成された有機化合物の第二加熱固定被覆を有する被覆粉体、
(2)粉体と第一被覆有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理して、粉体表面の少なくとも一部に第一加熱固定被覆を形成する工程と、前記の工程で得られた粉体と第二被覆有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理して、その第一加熱固定被覆の上の少なくとも一部に第二加熱固定被覆を形成する工程とを含む、被覆粉体の製造方法、
(3)前記(1)に記載の被覆粉体を含む分散体、
(4)前記(1)に記載の被覆粉体を含む化粧料、などである。
That is, the present invention provides: (1) a first heat-fixed coating of an organic compound formed on at least a part of the powder surface and a second organic compound formed on at least a part of the first heat-fixed coating. Coated powder having a heat-fixed coating,
(2) The powder and the first coating organic compound are pulverized in an airflow pulverizer and then heat-treated to form a first heat-fixed coating on at least a part of the powder surface; A step of forming the second heat-fixed coating on at least a part of the first heat-fixed coating after the obtained powder and the second coating organic compound are pulverized in an airflow pulverizer and then heat-treated; A method for producing a coated powder,
(3) A dispersion containing the coated powder according to (1),
(4) Cosmetics containing the coated powder according to (1).
本発明は、有機化合物の第一加熱固定被覆、第二加熱固定被覆を施した粉体であって、長期間の油性分散安定性、疎水安定性等に優れているため、種々の用途に用いることができる。例えば、本発明の被覆粉体を溶媒に分散した分散体や化粧料に配合すると長期間の安定した使用が可能であり、また、粉体の高濃度化も可能となる。
また、本発明は、被覆粉体の製造方法であり、粉体と有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理する工程を二回行って第一加熱固定被覆、第二加熱固定被覆を施すことによって一層強固な被覆が得られる。
The present invention is a powder having a first heat-fixed coating and a second heat-fixed coating of an organic compound, and is excellent in long-term oil dispersion stability, hydrophobic stability, etc. be able to. For example, when the coated powder of the present invention is blended with a dispersion in which a solvent is dispersed or a cosmetic, it can be used stably for a long period of time, and the concentration of the powder can be increased.
Further, the present invention is a method for producing a coated powder, wherein the powder and the organic compound are pulverized in an airflow pulverizer and then heat-treated twice to perform the first heat-fixed coating and the second heat-fixed. By applying the coating, a stronger coating can be obtained.
本発明は、粉体表面の少なくとも一部に形成された有機化合物の第一加熱固定被覆及びその第一加熱固定被覆の上の少なくとも一部に形成された有機化合物の第二加熱固定被覆を有する被覆粉体である。 The present invention has a first heat-fixed coating of an organic compound formed on at least a part of the powder surface and a second heat-fixed coating of an organic compound formed on at least a part of the first heat-fixed coating. It is a coated powder.
粉体としては、種々の物質を用いることができ、例えば、体質顔料として、マイカ、セリサイト、タルク、クレー、カオリン、合成マイカ、炭酸カルシウム、炭酸マグネシウム、ケイ酸マグネシウム、ケイ酸アルミニウム、リン酸カルシウム、無水ケイ酸、アルミナ、酸化マグネシウム、酸化ジルコニウム、水酸化アルミニウム、硫酸バリウム、ケイ酸アルミン酸マグネシウム、メタケイ酸アルミン酸マグネシウム、窒化ホウ素、ゼオライト、ヒドロキシアパタイト、セラミックパウダー等を挙げることができる。また、白色顔料としては、塩基性炭酸鉛、塩基性硫酸鉛、酸化チタン、酸化亜鉛、酸化セリウム、リン酸亜鉛、リン酸アルミニウム等を、着色顔料としては、ベンガラ、黄酸化鉄、黒酸化鉄、酸化コバルト、酸化クロム、水酸化クロム、紺青、群青、カーボンブラック、低次酸化チタン、マンゴバイオレット、亜酸化銅、黒鉛、黄鉛、カドミウムエロー、カドミウムレッド、コバルトブルー、モリブデートオレンジ等を、蛍光顔料としては、硫化亜鉛、珪酸亜鉛、硫酸亜鉛カドミウム、硫化カルシウム、硫化ストロンチウム、タングステン酸カルシウム等を、パール顔料としては、オキシ塩化ビスマス、雲母チタン、魚鱗箔等を、微粒子粉体としては、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化鉄、微粒子酸化セリウム等を、金属光沢顔料としては、アルミニウムパウダー、亜鉛粉、金粉、銀粉、スズ粉、ステンレスパウダー、ダイヤモンドパウダー、銅粉、ニッケルパウダー、ブロンズパウダー等を、蛍光顔料としては硫化亜鉛、タングステン酸カルシウム等を、その他の粉体としては、酸化錫、ATO(アンチモンドープ酸化錫)、ITO(錫ドープ酸化インジウム)、Alドープ酸化亜鉛等をそれぞれ挙げることができる。また、必要に応じてこれらの粉体を複合化したもの又は無機化合物で被覆したものを用いることができる。例えば、微粒子酸化チタン、微粒子酸化亜鉛、微粒子酸化鉄、微粒子酸化セリウム等の微粒子粉体をアルミニウム、カルシウム、マグネシウム、セリウム、ケイ素、ジルコニウム、チタン、亜鉛、鉄、コバルト、マンガン、ニッケル及びスズの少なくとも1種の酸化物又は含水酸化物で被覆した粉体、ベンガラ等の無機着色顔料を無水ケイ酸で被覆した粉体、体質顔料を微粒子白色顔料で被覆した粉体等が挙げられる。 As the powder, various substances can be used. For example, as an extender pigment, mica, sericite, talc, clay, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicate, calcium phosphate, Examples thereof include anhydrous silicic acid, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, barium sulfate, magnesium aluminate silicate, magnesium aluminate metasilicate, boron nitride, zeolite, hydroxyapatite, and ceramic powder. White pigments include basic lead carbonate, basic lead sulfate, titanium oxide, zinc oxide, cerium oxide, zinc phosphate, and aluminum phosphate, and color pigments include bengara, yellow iron oxide, and black iron oxide. , Cobalt oxide, chromium oxide, chromium hydroxide, bitumen, ultramarine, carbon black, low order titanium oxide, mango violet, cuprous oxide, graphite, chrome lead, cadmium yellow, cadmium red, cobalt blue, molybdate orange, etc. As fluorescent pigments, zinc sulfide, zinc silicate, cadmium zinc sulfate, calcium sulfide, strontium sulfide, calcium tungstate, etc., as pearl pigments, bismuth oxychloride, titanium mica, fish scale foil, etc. Fine metallic titanium oxide, fine zinc oxide, fine iron oxide, fine cerium oxide, etc. Aluminum powder, zinc powder, gold powder, silver powder, tin powder, stainless steel powder, diamond powder, copper powder, nickel powder, bronze powder, etc. as the material, zinc sulfide, calcium tungstate, etc. as the fluorescent pigment, and other powders Examples of the body include tin oxide, ATO (antimony-doped tin oxide), ITO (tin-doped indium oxide), and Al-doped zinc oxide. In addition, a composite of these powders or a coating with an inorganic compound can be used as necessary. For example, fine particle powders such as fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide, fine particle cerium oxide are made of at least aluminum, calcium, magnesium, cerium, silicon, zirconium, titanium, zinc, iron, cobalt, manganese, nickel and tin. Examples thereof include powders coated with one kind of oxide or hydrous oxide, powders coated with inorganic colored pigments such as Bengala with silicic anhydride, and powders coated with extender pigments with fine white pigments.
本発明の被覆粉体は、粉体表面の少なくとも一部に特定の有機化合物を被覆するが、有機化合物を加熱により粉体表面に固定する被覆(以下、加熱固定被覆と称する。)であり、第一加熱固定被覆、その第一加熱固定被覆の上の少なくとも一部に形成された第二加熱固定被覆の二層を備える。第一加熱固定被覆量、第二加熱固定被覆量は適宜設定することができ、合計量で粉体の重量に対して5〜30重量%程度が好ましく、10〜25重量%がより好ましく、15〜25重量%が更に好ましい。また、第一加熱固定被覆と第二加熱固定被覆の被覆比は、それぞれの重量比で5/10〜10/10が好ましく、5/10〜8/10がより好ましく、5/10〜7/10が更に好ましい。 The coated powder of the present invention is a coating (hereinafter referred to as heat-fixed coating) in which a specific organic compound is coated on at least a part of the powder surface, and the organic compound is fixed to the powder surface by heating. A first heat-fixed coating and two layers of a second heat-fixed coating formed on at least a part of the first heat-fixed coating are provided. The first heat-fixed coating amount and the second heat-fixed coating amount can be appropriately set, and the total amount is preferably about 5 to 30% by weight, more preferably 10 to 25% by weight based on the weight of the powder, 15 More preferred is ˜25% by weight. Further, the coating ratio of the first heat-fixed coating and the second heat-fixed coating is preferably 5/10 to 10/10, more preferably 5/10 to 8/10, and 5/10 to 7 / in weight ratio. 10 is more preferable.
前記の第一加熱固定被覆を形成する第一被覆有機化合物は、ポリシロキサン、アルコキシシラン、アルキルシラン、脂肪酸又はその塩、ポリオレフィン、水添レシチン又はその塩、N−アシルアミノ酸又はその塩、デキストリン脂肪酸エステルから選ばれる少なくとも一種が好ましい。また、前記の第二加熱固定被覆を形成する第一被覆有機化合物は、ポリシロキサン、アルコキシシラン、アルキルシラン、脂肪酸又はその塩、ポリオレフィン、水添レシチン又はその塩、N−アシルアミノ酸又はその塩、デキストリン脂肪酸エステルから選ばれる少なくとも一種が好ましい。 The first coating organic compound forming the first heat-fixed coating is polysiloxane, alkoxysilane, alkylsilane, fatty acid or salt thereof, polyolefin, hydrogenated lecithin or salt thereof, N-acyl amino acid or salt thereof, dextrin fatty acid At least one selected from esters is preferred. The first coating organic compound forming the second heat-fixed coating is polysiloxane, alkoxysilane, alkylsilane, fatty acid or salt thereof, polyolefin, hydrogenated lecithin or salt thereof, N-acylamino acid or salt thereof, At least one selected from dextrin fatty acid esters is preferred.
ポリシロキサンは、ジクロロジメチルシラン等のシラン類を加水分解し、生成したシラノールが脱水縮合したオリゴマー又はポリマーである。ポリシロキサンとしては例えば、ジメチルポリシロキサン、ジメトキシポリシロキサン、変性オルガノポリシロキサン等のオルガノポリシロキサン、メチルハイドロジェンポリシロキサン等のオルガノハイドロジェンポリシロキサン、メチルハイドロジェンシロキサン−ジメチルシロキサン共重合体等のシロキサンコポリマー、シリコーンポリマー、トリオルガノシロキシケイ酸などのシラノールが脱水縮合したオリゴマー又はポリマーを含む化合物である。 Polysiloxane is an oligomer or polymer obtained by hydrolyzing silanes such as dichlorodimethylsilane and dehydrating condensation of the generated silanol. Examples of the polysiloxane include organopolysiloxanes such as dimethylpolysiloxane, dimethoxypolysiloxane, modified organopolysiloxane, organohydrogenpolysiloxanes such as methylhydrogenpolysiloxane, and siloxanes such as methylhydrogensiloxane-dimethylsiloxane copolymer. It is a compound containing an oligomer or polymer obtained by dehydration condensation of a silanol such as a copolymer, a silicone polymer, or triorganosiloxysilicic acid.
具体的には、オルガノポリシロキサンとしては、ジメチルポリシロキサンが挙げられ、それはジメチコンともいわれ、その基本化学構造は、次の一般式(I)で表される。一般式(I)におけるnが、n=1〜400のものが好ましく、粘度は概ね1〜1000センチストークスのものが好ましい。 Specifically, examples of the organopolysiloxane include dimethylpolysiloxane, which is also called dimethicone, and its basic chemical structure is represented by the following general formula (I). In general formula (I), n is preferably n = 1 to 400, and the viscosity is preferably about 1 to 1000 centistokes.
また、オルガノハイドロジェンポリシロキサンとしては、メチルハイドロジェンポリシロキサン等が挙げられ、重合度nが3〜7の整数であることがより好ましい。シロキサンコポリマーとしては、メチルハイドロジェンシロキサン−ジメチルシロキサン共重合体等が挙げられ、それはジメチコン/メチコンコポリマーともいわれ、その基本化学構造は、次の一般式(II)で表され、本発明においては、一般式(II)におけるm、nが、m=7〜14、n=3〜8であり、m+nが、m+n=10〜22のものが好ましい。 Examples of the organohydrogenpolysiloxane include methylhydrogenpolysiloxane, and the polymerization degree n is more preferably an integer of 3 to 7. Examples of the siloxane copolymer include a methylhydrogensiloxane-dimethylsiloxane copolymer, which is also called a dimethicone / methicone copolymer, and its basic chemical structure is represented by the following general formula (II). In the present invention, In the general formula (II), m and n are preferably m = 7 to 14, n = 3 to 8, and m + n is preferably m + n = 10 to 22.
また、アルコキシシランとしては、メチルトリメトキシシラン、エチルトリエトキシシラン、オクチルトリエトキシシラン等が挙げられる。アルキルシランとしては、メチルシラン、エチルシラン、オクチルシラン等が挙げられる。脂肪酸としては、例えばカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、イソミリスチン酸、パルミチン酸、イソパルミチン酸、ステアリン酸、イソステアリン酸、アラキン酸、ウンデシレン酸、オレイン酸、ミリストレイン酸、エライジン酸、リノール酸、リノレン酸、アラキドン酸、ヤシ油脂肪酸、牛脂脂肪酸、樹脂酸(アビエチン酸)、それらの塩、それらの金属塩等を挙げることができる。また、トリメチルシロキシケイ酸は、水ガラスのナトリウムをトリメチルシリル基で置換して得られたものを溶媒に溶解したものである。 Examples of the alkoxysilane include methyltrimethoxysilane, ethyltriethoxysilane, octyltriethoxysilane, and the like. Examples of the alkyl silane include methyl silane, ethyl silane, octyl silane and the like. Examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, arachidic acid, undecylenic acid, oleic acid, myristoleic acid, elaidic acid, Examples thereof include linoleic acid, linolenic acid, arachidonic acid, coconut oil fatty acid, beef tallow fatty acid, resin acid (abietic acid), salts thereof, and metal salts thereof. Further, trimethylsiloxysilicic acid is obtained by dissolving water glass sodium obtained by substituting sodium with a trimethylsilyl group in a solvent.
また、ポリオレフィンとしてはポリエチレン、ポリプロピレン等を用いることができ、例えば、分子量500〜20000で融点が40℃以上の低分子ポリエチレンや、ポリプロピレンを酸化して得られる酸化ポリエチレン、マレイン化ポリエチレン、酸化ポリプロピレン等の市販品を使用することができる。 In addition, polyethylene, polypropylene, and the like can be used as the polyolefin. For example, low molecular polyethylene having a molecular weight of 500 to 20000 and a melting point of 40 ° C. or more, polyethylene oxide obtained by oxidizing polypropylene, maleated polyethylene, polypropylene oxide, and the like. Commercial products can be used.
水添レシチンとしては、卵黄、大豆、コーン、菜種等から抽出された天然のレシチンや合成レシチンを水素添加したもので、ヨウ素価が好ましくは30以下、より好ましくは15以下の水添レシチンであり、リン酸基を有するグリセライドである。塩の形態にあるものとしては、Al、Mg、Ca、Zn、Zr、Ti等の水不溶性水添レシチン金属塩が好ましい。 Hydrogenated lecithin is a hydrogenated natural lecithin or synthetic lecithin extracted from egg yolk, soybean, corn, rapeseed, etc., and has an iodine value of preferably 30 or less, more preferably 15 or less. And a glyceride having a phosphate group. As the salt form, a water-insoluble hydrogenated lecithin metal salt such as Al, Mg, Ca, Zn, Zr and Ti is preferable.
また、N−アシルアミノ酸は、アミノ酸のアミノ基及び/又はイミノ基がアシル化されたものである。アミノ酸の種類としては、グリシン、アラニン、β−アラニン、バリン、ロイシン、イソロイシン、フェニルアラニン、プロリン、スレオニン、セリン、アルギニン、ヒスチジン、リジン、アスパラギン酸、グルタミン酸、チロシン、メチオニン、シスチン、システイン等を挙げることができる。 N-acylamino acids are those in which the amino group and / or imino group of the amino acid is acylated. Examples of amino acid types include glycine, alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, threonine, serine, arginine, histidine, lysine, aspartic acid, glutamic acid, tyrosine, methionine, cystine, cysteine, etc. Can do.
N−アシル体を構成する脂肪酸は、長鎖脂肪酸が好ましく、例えばカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、イソミリスチン酸、パルミチン酸、イソパルミチン酸、ステアリン酸、イソステアリン酸、アラキン酸、ウンデシレン酸、オレイン酸、ミリストレイン酸、エライジン酸、リノール酸、リノレン酸、アラキドン酸、ヤシ油脂肪酸、牛脂脂肪酸、樹脂酸(アビエチン酸)等を挙げることができる。塩の形態としてはNa、K、Ba、Zn、Ca、Mg、Fe、Zr、Co、Al、Zr、Ti等の金属塩や、アンモニウム塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、2−アミノ−2−メチル−プロパノール、2−アミノ−2−メチル−1,3−プロパンジオール、トリイソプロパノールアミン等の各種アルカノールアミン塩等を挙げることができる。 The fatty acid constituting the N-acyl is preferably a long-chain fatty acid. Examples thereof include acid, oleic acid, myristoleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, coconut oil fatty acid, beef tallow fatty acid, and resin acid (abietic acid). As salt forms, metal salts such as Na, K, Ba, Zn, Ca, Mg, Fe, Zr, Co, Al, Zr, Ti, ammonium salts, monoethanolamine, diethanolamine, triethanolamine, 2-amino Examples thereof include various alkanolamine salts such as 2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, and triisopropanolamine.
また、デキストリン脂肪酸エステルとしては、デキストリンと脂肪酸とで構成されるエステル或いはその誘導体から選択することができる。好ましくは、デキストリン1分子に対し、その水酸基の1つに炭素数8〜24の脂肪酸の1分子がエステル化した部分構造を少なくとも有するエステル体或いはその誘導体、例えばデキストリン1分子に対し炭素数8〜24の脂肪酸が1個又は複数個、その水酸基の1個又は複数個にエステル結合した構造を有するエステル体や当該エステル体において水酸基が更に別種の脂肪酸でエステル化された誘導体等を挙げることができる。 Moreover, as dextrin fatty acid ester, it can select from the ester comprised with dextrin and a fatty acid, or its derivative (s). Preferably, for one dextrin molecule, an ester having at least a partial structure in which one molecule of a fatty acid having 8 to 24 carbon atoms is esterified to one of its hydroxyl groups, or a derivative thereof, such as 8 to 8 carbon atoms for one molecule of dextrin Examples include ester bodies having a structure in which one or a plurality of 24 fatty acids and one or more of the hydroxyl groups are ester-bonded, and derivatives in which the hydroxyl groups are further esterified with another fatty acid. .
本発明においては、第一加熱固定被覆が少なくともメチルハイドロジェンシロキサン−ジメチルシロキサン共重合体を含む被覆であり、第二加熱固定被覆が少なくともジメチルポリシロキサンを含む被覆であるのがより好ましい。メチルハイドロジエンシロキサン−ジメチルシロキサン共重合体は、上記一般式(II)のとおり水素基を有しているため、粉体表面に水素結合により被覆され、更に、残る水素基とジメチルポリシロキサンとの結合により、二層の強固な被覆が形成される。 In the present invention, it is more preferable that the first heat-fixed coating is a coating containing at least a methylhydrogensiloxane-dimethylsiloxane copolymer, and the second heat-fixed coating is a coating containing at least dimethylpolysiloxane. Since the methylhydrodienesiloxane-dimethylsiloxane copolymer has hydrogen groups as shown in the general formula (II), the powder surface is coated with hydrogen bonds, and the remaining hydrogen groups and dimethylpolysiloxane are further coated. The bond forms a two-layer strong coating.
次に、本発明は、粉体と第一被覆有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理して、粉体表面の少なくとも一部に第一加熱固定被覆を形成する工程と、前記の工程で得られた粉体と第二被覆有機化合物とを気流粉砕機に入れ粉砕した後、加熱処理して、その第一加熱固定被覆の上の少なくとも一部に第二加熱固定被覆を形成する工程とを含む、被覆粉体の製造方法である。 Next, the present invention includes a step of forming the first heat-fixed coating on at least a part of the powder surface by pulverizing the powder and the first coating organic compound in an airflow pulverizer, The powder obtained in the above step and the second coating organic compound are pulverized in an airflow pulverizer and then heat-treated, and the second heat-fixed coating is applied to at least a part of the first heat-fixed coating. Forming a coated powder including a forming step.
まず、粉体と第一被覆有機化合物とを気流粉砕機に入れ粉砕する。気流粉砕機は、高速でアルゴンガスや窒素ガス等をノズルから噴出させ、このガス流によって粉末粒子を加速、互いに衝突させて粉砕する機械であり、ジェットミル、クロスジェットミル、セレンミラー等を用いることができる。 First, the powder and the first coating organic compound are put in an airflow pulverizer and pulverized. An airflow pulverizer is a machine that jets argon gas, nitrogen gas, or the like from a nozzle at high speed, and accelerates powder particles by this gas flow and collides with each other to pulverize them, using a jet mill, a cross jet mill, a selenium mirror, etc. be able to.
次に、粉砕物を加熱する処理を行う。第一加熱処理の温度、時間は適宜設定することができ、加熱温度は50〜300℃が好ましく、100〜200℃がより好ましく、120〜170℃が更に好ましい。加熱時間は0.5〜12時間が好ましい。加熱雰囲気は酸素ガス、大気中等の酸化性雰囲気、窒素ガス、アルゴンガス等の不活性ガス雰囲気、水素ガス等の還元性ガス雰囲気のいずれでもよく、特に不活性ガス雰囲気が好ましい。この第一加熱処理により、粉砕物を乾燥させるとともに、第一加熱固定被覆を形成する。 Next, the process which heats a ground material is performed. The temperature and time of the first heat treatment can be appropriately set, and the heating temperature is preferably 50 to 300 ° C, more preferably 100 to 200 ° C, and still more preferably 120 to 170 ° C. The heating time is preferably 0.5 to 12 hours. The heating atmosphere may be any of an oxygen gas, an oxidizing atmosphere such as air, an inert gas atmosphere such as nitrogen gas and argon gas, and a reducing gas atmosphere such as hydrogen gas, and an inert gas atmosphere is particularly preferable. By this first heat treatment, the pulverized product is dried and a first heat-fixed coating is formed.
次いで、第一加熱固定被覆した粉体は、第二被覆有機化合物と前記の気流粉砕機に入れ粉砕した後、第二加熱処理する。第二加熱処理の温度、時間は適宜設定することができ、加熱温度は50〜300℃が好ましく、100〜200℃がより好ましく、120〜170℃が更に好ましい。加熱時間は0.5〜12時間が好ましい。加熱雰囲気は酸素ガス、大気中等の酸化性雰囲気、窒素ガス、アルゴンガス等の不活性ガス雰囲気、水素ガス等の還元性ガス雰囲気のいずれでもよく、特に不活性ガス雰囲気が好ましい。この第二加熱処理により、粉砕物を乾燥させるとともに、第二加熱固定被覆を形成する。 Next, the first heat-fixed powder is pulverized in the second coating organic compound and the airflow pulverizer and then subjected to the second heat treatment. The temperature and time of the second heat treatment can be appropriately set, and the heating temperature is preferably 50 to 300 ° C, more preferably 100 to 200 ° C, and still more preferably 120 to 170 ° C. The heating time is preferably 0.5 to 12 hours. The heating atmosphere may be any of an oxygen gas, an oxidizing atmosphere such as air, an inert gas atmosphere such as nitrogen gas and argon gas, and a reducing gas atmosphere such as hydrogen gas, and an inert gas atmosphere is particularly preferable. By this second heat treatment, the pulverized product is dried and a second heat-fixed coating is formed.
第一被覆有機化合物、第二被覆有機化合物としては、前記の有機化合物を用いることができ、第一被覆有機化合物としては少なくともメチルハイドロジェンシロキサン−ジメチルシロキサン共重合体がより好ましく、第二被覆有機化合物としては少なくともジメチルポリシロキサンがより好ましい。 As the first coating organic compound and the second coating organic compound, the above-mentioned organic compounds can be used, and as the first coating organic compound, at least a methylhydrogensiloxane-dimethylsiloxane copolymer is more preferable. The compound is more preferably at least dimethylpolysiloxane.
なお、気流粉砕機に入れる前に、粉体と第一被覆有機化合物又は第二被覆有機化合物とを混合させるのが好ましく、ヘンシルミキサーやスーパーミキサー等の混合機、ボールミルやサンドグラインダー等のミルで混合するのが好ましい。混合条件は適宜設定することができ、例えば、混合温度は室温が好ましく、混合雰囲気は酸素ガス、大気中等の酸化性雰囲気、窒素ガス、アルゴンガス等の不活性ガス雰囲気、水素ガス等の還元性ガス雰囲気のいずれでもよく、特に不活性ガス雰囲気が好ましい。 In addition, it is preferable to mix the powder and the first coated organic compound or the second coated organic compound before entering the airflow grinder, a mixer such as a Hensyl mixer or a super mixer, a mill such as a ball mill or a sand grinder. Are preferably mixed together. The mixing conditions can be appropriately set. For example, the mixing temperature is preferably room temperature, the mixing atmosphere is an oxygen gas, an oxidizing atmosphere such as air, an inert gas atmosphere such as nitrogen gas or argon gas, and a reducing property such as hydrogen gas. Any gas atmosphere may be used, and an inert gas atmosphere is particularly preferable.
次に、本発明は、前記の被覆粉体を含む分散体であり、被覆粉体を分散媒に分散したものである。 Next, the present invention is a dispersion containing the above-mentioned coated powder, in which the coated powder is dispersed in a dispersion medium.
被覆粉体の濃度は適宜調整することができるが、より高い濃度が好ましい。具体的には、10〜75重量%が好ましく、10〜65重量%がより好ましく、30〜60重量%が更に好ましい。 The concentration of the coating powder can be adjusted as appropriate, but a higher concentration is preferable. Specifically, 10 to 75% by weight is preferable, 10 to 65% by weight is more preferable, and 30 to 60% by weight is still more preferable.
分散媒としては、特に限定されず、適宜種々のもの用いることができ、親油性分散媒を好適に用いることができる。具体的には、エタノール、プロピルアルコール、イソプロピルアルコール、ブタノール、アミルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、カプリルアルコール、ノニルアルコール、デシルアルコール、フェノール、ベンジルアルコール等の一価アルコール系溶剤類、ノルマルペンタン、ノルマルヘキサン、ノルマルヘプタン、ノルマルオクタン、イソヘキサン、イソオクタン、ガソリン、ミネラルスピリット等の石油系炭化水素類、ベンゼン、トルエン、キシレン、シクロヘキサン、エチルベンゼン、アミルベンゼン等の芳香属炭化水素系溶剤類、ジペンテン、テレビン油等の植物系炭化水素系溶剤類、ニトロパラフィン、ニトロベンゼン等のニトロ炭化水素系溶剤類、アセトン、メチルエチルケトン、メチルイソブチルケトン、エチルブチルケトン、ジイソブチルケトン等のケトン系溶剤類、塩化メチレン、クロロホルム、四塩化炭素、パークロルエチレン、モノクロルベンゼン等のハロゲン化炭化水素系溶剤類、エチルエーテル、イソプロピルエーテル、ブチルエーテル、ヘキシルエーテル、プロピレンオキシド、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル等のエーテル系溶剤類、ぎ酸メチル、ぎ酸エチル、ぎ酸ブチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸アミル、プロピオン酸エチル、プロピオン酸ブチル、プロピオン酸イソブチル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、乳酸ブチル、乳酸アミル等のエステル系溶剤類、サフラワー油、大豆油、月見草油、ブドウ種子油、ローズヒップ油、ククイナッツ油、アルモンド油、ゴマ油、コムギ胚芽油、トウモロコシ油、綿実油、アボガド油、オリーブ油、ツバキ油、パーシック油、ヒマシ油、ラッカセイ油、ヘーゼルナッツ油、マカデミアナッツ油、メドフォーム油、カカオ脂、シア脂、木ロウ、ヤシ油、パーム油、パーム核油、牛脂、馬脂、ミンク油、乳脂、卵黄油、タートル油等の油脂類、流動パラフィン、流動イソパラフィン、スクワラン、スクワレン、ワセリン、パラフィン、セレシン、マイクロクリスタリンワックス等の炭化水素油類、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、オレイン酸、リノール酸、ウンデシレン酸、ヒドロキシステアリン酸、ラノリン脂肪酸等の脂肪酸、ミリスチルアルコール、セチルアルコール、セトステアリルアルコール、ステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、オレイルアルコール、ホホバアルコール、バチルアルコール、コレステロール、フィトステロール、ラノリンアルコール、イソステアリルアルコール等の高級アルコール類、イソステアリン酸イソプロピル、オレイン酸エチル、ミリスチン酸イソプロピル、パルミチン酸イソイソプロピル、オクタン酸セチル、リンゴ酸ジイソステアリル、トリカプリル酸グリセリル、イソノナン酸イソオクチル、イソノナン酸イソノニル、イソノナン酸イソトリデシル、ネオペンタン酸オクチルドデシル、ネオペンタン酸イソトリデシル、ネオペンタン酸ミリスチル、ジイソノナン酸プロピレングリコール、トリ2−エチルヘキサン酸グリセリル、トリ2−エチルヘキサン酸トリメチロールプロパン等のエステル油類、ミツロウ、カンデリラロウ、鯨ロウ、綿ロウ、カルナウバロウ、ベイベリーロウ、ヌカロウ、イボタロウ、オレンジラッフィー油、モンタンロウ、サトウキビロウ、セラックロウ、ラノリン、ホホバオイル、等のロウ類、メチルポリシロキサン、メチルフェニルポリシロキサン、デカメチルシクロテトラシロキサン、アルキル変性シリコーン、アルコール変性シリコーン、アミノ変性シリコーン、エポキシ変性シリコーン、オレフィン変性シリコーン、カルボキシル変性シリコーン、カルビノール変性シリコーン、フェノール変性シリコーン、メタクリル変性シリコーン、メルカプト変性シリコーン、リン酸変性シリコーン、フッ素変性シリコーン、高級脂肪酸変性シリコーン、ポリエーテル変性シリコーン等のシリコーン類、パーフルオロポリエーテル、ハイドロフルオロエーテル、パーフルオロメチルシクロペンタン、パーフルオロジメチルシクロヘキサン、パーフルオロジメチルシクロブタン、メトキシノナフルオロブタン、エトキシノナフルオロブタン、ドデカフルオロペンタン、テトラデカフルオロヘキサン、パーフルオロデカン、パーフルオロオクタン、4−トリトリフルオロメチルパーフルオロモルホリン、4−ペンタフルオロエチルパーフルオロモルホリン等のフッ素系油剤、UV吸収剤としてパラアミノ安息香酸、パラアミノ安息香酸モノグリセリンエステル、N,N−ジメチルパラアミノ安息香酸エチルエステル、N,N−ジエトキシパラアミノ安息香酸エチルエステル、N,N−ジプロポキシパラアミノ安息香酸エチルエステル等の安息香酸類、ホモメンチル−N−アセチルアントラニレート等のアントラニル酸類、アミルサリシレート、メンチルサリシレート、ホモメンチルサリシレート、オクチルサリシレート、フェニルサリシレート、ベンジルサリシレート等のサリチル酸類、オクチルシンナメート、エチル−4−イソプロピルシンナメート、メチル−2,5−ジイソプロピルシンナメート、エチル−2,4−ジイソプロピルシンナメート、プロピル−p−メトキシシンナメート、イソプロピル−p−メトキシシンナメート、イソアミル−p−メトキシシンナメート、オクチル−p−メトキシシンナメート、2−エトキシエチル−p−メトキシシンナメート、シクロヘキシル−p−メトキシシンナメート等の桂皮酸類、2,4−ジヒドロキシベンゾフェノン、2,2'−ジヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸塩、4−フェニルベンゾフェノン、4−ヒドロキシ−3−カルボキシベンゾフェノン等のベンゾフェノン類、3−ベンジリデン−d,l−カンファー、ウロカニン酸、ウロカニン酸エチルエステル、2−フェニル−5−メチルベンゾキサゾール、ジベンザラジン、ジアニソイルメタン、4−tert−ブチル−4'−メトキシジベンゾイルメタン、シリコーン変性紫外線吸収剤、フッ素変性紫外線吸収剤等が挙げられる。これらのうち1種又は2種以上を本発明において親油性溶媒として使用できる。 The dispersion medium is not particularly limited, and various types can be used as appropriate, and a lipophilic dispersion medium can be suitably used. Specifically, monohydric alcohol solvents such as ethanol, propyl alcohol, isopropyl alcohol, butanol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, phenol and benzyl alcohol, normal Petroleum hydrocarbons such as pentane, normal hexane, normal heptane, normal octane, isohexane, isooctane, gasoline, mineral spirits, aromatic hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane, ethylbenzene, amylbenzene, dipentene , Plant hydrocarbon solvents such as turpentine oil, nitro hydrocarbon solvents such as nitroparaffin and nitrobenzene, acetone, methyl ethyl ketone, Ketone solvents such as til isobutyl ketone, ethyl butyl ketone, diisobutyl ketone, halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, perchlorethylene, monochlorobenzene, ethyl ether, isopropyl ether, butyl ether, Ether solvents such as hexyl ether, propylene oxide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, acetic acid Ester solvents such as amyl, ethyl propionate, butyl propionate, isobutyl propionate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, butyl lactate, amyl lactate, safra -Oil, soybean oil, evening primrose oil, grape seed oil, rosehip oil, cucumber nut oil, almond oil, sesame oil, wheat germ oil, corn oil, cottonseed oil, avocado oil, olive oil, camellia oil, persic oil, castor oil, peanut oil Oils such as hazelnut oil, macadamia nut oil, medofoam oil, cocoa butter, shea butter, tree wax, coconut oil, palm oil, palm kernel oil, beef tallow, horse fat, mink oil, milk fat, egg yolk oil, turtle oil, Liquid paraffin, liquid isoparaffin, squalane, squalene, petrolatum, paraffin, ceresin, microcrystalline wax and other hydrocarbon oils, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, undecylenic acid, Fatty acids such as hydroxystearic acid and lanolin fatty acid, milli Still alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, jojoba alcohol, batyl alcohol, higher alcohols such as cholesterol, phytosterol, lanolin alcohol, isostearyl alcohol, isopropyl isostearate, ethyl oleate , Isopropyl myristate, isoisopropyl palmitate, cetyl octanoate, diisostearyl malate, glyceryl tricaprylate, isooctyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, octyldodecyl neopentanoate, isotridecyl neopentanoate, myristyl neopentanoate, diisononane Propylene glycol acid, tri-2- Ester oils such as glyceryl tilhexanoate, trimethylolpropane tri-2-ethylhexanoate, beeswax, candelilla wax, whale wax, cotton wax, carnauba wax, bayberry wax, nukarou, ibotarou, orange luffy oil, montan wax, sugarcane wax, shellac wax, lanolin , Jojoba oil, waxes, methylpolysiloxane, methylphenylpolysiloxane, decamethylcyclotetrasiloxane, alkyl-modified silicone, alcohol-modified silicone, amino-modified silicone, epoxy-modified silicone, olefin-modified silicone, carboxyl-modified silicone, carbinol Modified silicone, phenol modified silicone, methacryl modified silicone, mercapto modified silicone, phosphoric acid modified silicone, fluorine modified silicone Silicones such as corn, higher fatty acid-modified silicone, polyether-modified silicone, perfluoropolyether, hydrofluoroether, perfluoromethylcyclopentane, perfluorodimethylcyclohexane, perfluorodimethylcyclobutane, methoxynonafluorobutane, ethoxynonafluorobutane Fluorine oils such as dodecafluoropentane, tetradecafluorohexane, perfluorodecane, perfluorooctane, 4-trifluoromethylperfluoromorpholine, 4-pentafluoroethylperfluoromorpholine, paraaminobenzoic acid, paraamino as UV absorber Benzoic acid monoglycerin ester, N, N-dimethylparaaminobenzoic acid ethyl ester, N, N-diethoxyparaaminobenzoic acid ethyl Benzoic acids such as ethyl ester, N, N-dipropoxyparaaminobenzoic acid ethyl ester, anthranilic acids such as homomenthyl-N-acetylanthranilate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, etc. Salicylic acids, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinna Mate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate Cinnamic acids such as namate, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4 -Benzophenones such as phenylbenzophenone and 4-hydroxy-3-carboxybenzophenone, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, dibenzalazine, dianisoyl Examples thereof include methane, 4-tert-butyl-4′-methoxydibenzoylmethane, a silicone-modified ultraviolet absorber, a fluorine-modified ultraviolet absorber. Of these, one or more can be used as the lipophilic solvent in the present invention.
また、本発明の分散体には、顔料分散剤、油剤、界面活性剤、紫外線吸収剤、防腐剤、酸化防止剤、皮膜形成剤、保湿剤、増粘剤、染料、顔料、香料等を適宜配合することができる。 In addition, pigment dispersions, oils, surfactants, ultraviolet absorbers, preservatives, antioxidants, film forming agents, humectants, thickeners, dyes, pigments, fragrances and the like are appropriately added to the dispersion of the present invention. Can be blended.
例えばPOEラウリル硫酸トリエタノールアミン等のアルキルエーテル硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ラウリル硫酸ナトリウム、ラウリル硫酸カリウム等の高級アルキル硫酸エステル塩、N−アシルサルコシン酸、N−ミリストイル−N−メチルタウリンナトリウム等の高級脂肪酸アミドスルホン酸塩、硬化ヤシ油脂肪酸グリセリン硫酸ナトリウム等の高級脂肪酸エステル硫酸エステル塩、高級脂肪酸エステルスルホン酸塩、高級脂肪酸アルキロールアミド硫酸エステル塩、脂肪酸セッケン、スルホコハク酸塩、二級アルコール硫酸エステル塩、POEアルキルエーテルカルボン酸、POEアルキルアリルエーテルカルボン酸塩、α−オレフィンスルホン酸塩、ラウロイルモノエタノールアミドコハク酸ナトリウム、N−パルミトイルアスパラギン酸ジエタノールアミン、カゼインナトリウム等のアニオン系界面活性剤、塩化ステアリルトリメチルアンモニウム等のアルキルトリメチルアンモニウム塩、塩化ジステアリルジメチルアンモニウムジアルキルジメチルアンモニウム塩等のアルキルピリジニウム塩、アルキル四級アンモニウム塩、アルキルアミン塩、アルキルジメチルベンジルアンモニウム塩、アルキルイソキノリニウム塩、ジアルキルモリホニウム塩、POEアルキルアミン、ポリアミン脂肪酸誘導体、アミルアルコール脂肪酸誘導体、塩化ベンザルコニウム、塩化ベンゼトニウム等のカチオン系界面活性剤、2−ココイル−2−イミタゾリニウムヒドロキサイド−1−カルボキシエチロキシ2ナトリウム塩等のイミダゾリン系両性界面活性剤、アルキルベタイン、アミドベタイン、ラウリルジメチルアミノ酢酸ベタイン等のベタイン系両性界面活性剤、セスキオレイン酸グリセリン、モノステアリン酸グリセリン等のグリセリン脂肪酸エステル、ポリリシノール酸ヘキサグリセリル、モノステアリン酸ジグリセリル、デカオレイン酸デカグリセリル等のポリグリセリン脂肪酸エステル、ソルビタンモノオレート、ソルビタンセスキオレエート等のソルビタン脂肪酸エステル、モノステアリン酸プロピレングリコール等のプロピレングリコール脂肪酸エステル、POEソルビタンモノオレート等のPOEソルビタン脂肪酸エステル、POEグリセリントリイソステアレート等のPOEグリセリン脂肪酸エステル、POEモノオレート、POEジステアレート等のPOE脂肪酸エステル、POEラウリルエーテル、POEステアリルエーテル等のPOEアルキルエーテル、POE・POP水添ラノリン等のPOE・POPアルキルエーテル、硬化ひまし油誘導体、グリセリンアルキルエーテル、アルカノールアミド、ショ糖脂肪酸エステル、デキストリン脂肪酸エステル、でんぷん脂肪酸エステル、ヒドロキシステアリン酸等のノニオン系界面活性剤、その他レシチン等のリン脂質類、トレハロースリピド等の糖脂質類、パーフルオロアルキルリン酸塩、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルカルボン酸塩等のフッ素系界面活性剤等、アクリル酸メタクリル酸アルキル共重合体、ベントナイト、スメクタイト、カオリン等の天然又は合成の粘土鉱物、有機アミンカチオン変性ベントナイト等の有機変性粘土鉱物、アエロゾル等を挙げることができる。 For example, alkyl ether sulfates such as POE lauryl sulfate triethanolamine, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, higher alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate, N-acyl sarcosine acid, N- Higher fatty acid amide sulfonates such as sodium myristoyl-N-methyltaurine, higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid sodium glycerol sulfate, higher fatty acid ester sulfonates, higher fatty acid alkylolamide sulfates, fatty acid soaps , Sulfosuccinate, secondary alcohol sulfate, POE alkyl ether carboxylic acid, POE alkyl allyl ether carboxylate, α-olefin sulfonate, lauroyl mono Anionic surfactants such as sodium tanolamide succinate, N-palmitoyl aspartate diethanolamine, sodium caseinate, alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, alkylpyridinium salts such as distearyldimethylammonium dialkyldimethylammonium chloride, alkyl Quaternary ammonium salt, alkylamine salt, alkyldimethylbenzylammonium salt, alkylisoquinolinium salt, dialkyl morpholinium salt, POE alkylamine, polyamine fatty acid derivative, amyl alcohol fatty acid derivative, benzalkonium chloride, benzethonium chloride, etc. Cationic surfactant, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium Imidazoline-based amphoteric surfactants such as salts, betaine-based amphoteric surfactants such as alkylbetaine, amidebetaine, and lauryldimethylaminoacetic acid betaine, glycerin fatty acid esters such as glyceryl sesquioleate and glyceryl monostearate, hexaglyceryl polyricinoleate Polyglycerin fatty acid esters such as diglyceryl monostearate and decaglyceryl dekaoleate, sorbitan fatty acid esters such as sorbitan monooleate and sorbitan sesquioleate, propylene glycol fatty acid esters such as propylene glycol monostearate, POE sorbitan monooleate, etc. POE glycerin fatty acid ester such as POE sorbitan fatty acid ester, POE glycerin triisostearate, POE monooleate, POE dis POE fatty acid esters such as allate, POE alkyl ethers such as POE lauryl ether and POE stearyl ether, POE POP alkyl ethers such as POE / POP hydrogenated lanolin, hardened castor oil derivatives, glycerin alkyl ethers, alkanolamides, sucrose fatty acid esters, Dextrin fatty acid esters, starch fatty acid esters, nonionic surfactants such as hydroxystearic acid, phospholipids such as lecithin, glycolipids such as trehalose lipid, perfluoroalkyl phosphate, perfluoroalkyl sulfonate, Fluorine surfactants such as fluoroalkyl carboxylates, etc., alkyl methacrylate methacrylate copolymers, natural or synthetic clay minerals such as bentonite, smectite and kaolin, organic amine cuticles Organically-modified clay minerals such as down-modified bentonite, can be exemplified aerosol or the like.
本発明における被覆粉体を分散媒に混練又は混合分散させる方法は、公知の方法を採用すればよく特に限定されない。例えば、ニーダー混練、ヘンシル混練、ロール混練、エクストルーダー混練等の混練混合機、プロペラミキサー、ハイスピードミキサー、ディゾルバー、ホモジナイザー、アルテマイザー、湿式ジェットミル、コロイドミル、マスコロイダー、ビーズミル、サンドミル等の湿式混合分散機を使用して分散体を製造することができる。 The method for kneading or mixing and dispersing the coated powder in the dispersion medium in the present invention is not particularly limited as long as a known method is adopted. For example, kneader mixers such as kneader kneading, hensil kneading, roll kneading, extruder kneading, etc. A dispersion can be produced using a mixing and dispersing machine.
次に、本発明は、前記の被覆粉体を含む化粧料であり、前記の被覆粉体を配合して化粧料としたり、前記の分散体を用いて液体化粧料としたりしてもよい。例えば、パウダーファンデーション、リキッドファンデーション、油性ファンデーション、スティックファンデーション、プレストパウダー、フェイスパウダー、口紅、リップグロス、頬紅、アイシャドウ、アイブロウ、アイライナー、マスカラ、水性ネイルエナメル、油性ネイルエナメル、乳化型ネイルエナメル、エナメルトップコート、エナメルベースコート等の仕上用化粧品、エモリエントクリーム、コールドクリーム、美白クリーム、乳液、化粧水、美容液、カーマインローション、液状洗顔料、洗顔フォーム、洗顔クリーム、洗顔パウダー、メイククレンジング、ボディグロス等の皮膚用化粧品、ヘアーグロス、ヘアクリーム、ヘアーシャンプー、ヘアリンス、ヘアカラー、ヘアブラッシング剤等の頭髪用化粧品、その他として日焼け止め又は日焼け用クリームや乳液、石鹸、浴用剤、香水等を挙げることができる。 Next, the present invention is a cosmetic containing the above-described coated powder, and the above-mentioned coated powder may be blended to make a cosmetic, or the dispersion may be used to make a liquid cosmetic. For example, powder foundation, liquid foundation, oil foundation, stick foundation, pressed powder, face powder, lipstick, lip gloss, blusher, eye shadow, eyebrow, eyeliner, mascara, aqueous nail enamel, oily nail enamel, emulsified nail enamel, Finishing cosmetics such as enamel top coat, enamel base coat, emollient cream, cold cream, whitening cream, milky lotion, lotion, essence, carmine lotion, liquid facial cleanser, facial cleansing foam, facial cleansing cream, facial cleansing powder, makeup cleansing, body gloss Cosmetics for skin such as hair gloss, hair cream, hair shampoo, hair rinse, hair color, hair brushing agent, etc. Only stop or sunburn cream or milk, can be given soap, bath agent, perfume and the like.
被覆粉体の配合量は、化粧料の形態に応じて適宜配合することができ、例えば、液体化粧料には、1〜20重量%が好ましく、1〜15重量%がより好ましく、1〜10重量%が更に好ましい。本発明の化粧料には、通常配合されるものを用いることができ、例えば、顔料分散剤、油剤、界面活性剤、紫外線吸収剤、防腐剤、酸化防止剤、皮膜形成剤、保湿剤、増粘剤、染料、顔料、香料等を適宜配合することができる。 The blending amount of the coating powder can be appropriately blended according to the form of the cosmetic. For example, for a liquid cosmetic, 1 to 20% by weight is preferable, 1 to 15% by weight is more preferable, and 1 to 10%. More preferred is weight percent. For the cosmetics of the present invention, those usually blended can be used, for example, pigment dispersants, oils, surfactants, ultraviolet absorbers, preservatives, antioxidants, film forming agents, moisturizers, Adhesives, dyes, pigments, fragrances and the like can be appropriately blended.
本発明の被覆粉体、分散体は、化粧料以外の用途にも好適に用いることができ、プラスチックの添加剤、インク、塗料、トナー(磁性粉、外添剤)、化学繊維、包装材料、電子材料等の各種分野で広く使用される。
The coated powder and dispersion of the present invention can be suitably used for applications other than cosmetics, such as plastic additives, inks, paints, toners (magnetic powders, external additives), chemical fibers, packaging materials, Widely used in various fields such as electronic materials.
以下に本発明の実施例を示すが、本発明はこれらに制限されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
(実施例1)
微粒子酸化チタン(石原産業社製、TTO−S−3)1000gにメチルハイドロジエンシロキサン−ジメチルシロキサン共重合体(信越化学工業社製、KF−9901)75gを加え、ヘンシェルミキサー(三井鉱山社製)を用いて1800rpm、室温下窒素雰囲気で20分間混合した。次いで、混合物を気流粉砕機(セイシン企業社製)にて粉砕した後に、イナートオーブン(ヤマト科学社製、DN−4101)に入れ窒素雰囲気下150℃で30分間加熱処理を施し、第一加熱固定被覆粉体を得た。
Example 1
75g of methylhydrodienesiloxane-dimethylsiloxane copolymer (manufactured by Shin-Etsu Chemical Co., Ltd., KF-9901) is added to 1000g of fine particle titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., TTO-S-3), and Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Was mixed at 1800 rpm in a nitrogen atmosphere at room temperature for 20 minutes. Next, the mixture was pulverized with an airflow pulverizer (manufactured by Seishin Enterprise Co., Ltd.), then placed in an inert oven (manufactured by Yamato Kagaku Co., DN-4101), and subjected to heat treatment at 150 ° C. for 30 minutes in a nitrogen atmosphere, and first heat fixed A coated powder was obtained.
次に、得られた粉体1000gにジメチルポリシロキサン(信越化学工業社製、KF−96−100cs)70gを加え、ヘンシェルミキサー(三井鉱山社製)を用いて1800rpm、室温下窒素雰囲気下で20分間混合した。次いで、混合物を前記の気流粉砕機にて粉砕した後に、前記のイナートオーブンに入れ窒素雰囲気下150℃で30分間加熱処理を施して第二加熱固定被覆を形成して、本発明の被覆粉体(試料A)を得た。 Next, 70 g of dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-100cs) is added to 1000 g of the obtained powder, and the mixture is 20 at 1800 rpm in a nitrogen atmosphere at room temperature using a Henschel mixer (manufactured by Mitsui Mining). Mixed for minutes. Next, after the mixture is pulverized by the airflow pulverizer, the mixture is placed in the inert oven and heat-treated at 150 ° C. for 30 minutes in a nitrogen atmosphere to form a second heat-fixed coating. (Sample A) was obtained.
(比較例1)
実施例1の第一の工程において、微粒子酸化チタンとメチルハイドロジエンシロキサン−ジメチルシロキサン共重合体との混合物を気流粉砕機にて粉砕した後に、窒素雰囲気下150℃で30分間加熱処理を施こさないこと以外は、実施例1と同様に処理して、被覆粉体(試料B)を得た。
(Comparative Example 1)
In the first step of Example 1, a mixture of fine particle titanium oxide and methylhydrodienesiloxane-dimethylsiloxane copolymer was pulverized with an airflow pulverizer and then subjected to heat treatment at 150 ° C. for 30 minutes in a nitrogen atmosphere. A coated powder (Sample B) was obtained in the same manner as in Example 1 except that it was not.
(分散体の作製)
上記の方法で作製した試料A、Bそれぞれ100gを225ccマヨネーズ瓶に入れ、シクロペンタシロキサン(信越化学工業社製、KF−995)100gとガラスビーズを加え、ペイントシェーカーで30分間分散した。次に、ガラスビーズを濾別して試料Aを用いた本発明の分散体(試料C)と、試料Bを用いた比較用の分散体(試料D)を得た。
(Preparation of dispersion)
100 g of each of Samples A and B prepared by the above method was put in a 225 cc mayonnaise bottle, 100 g of cyclopentasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-995) and glass beads were added, and dispersed for 30 minutes with a paint shaker. Next, the glass beads were separated by filtration to obtain a dispersion of the present invention (sample C) using sample A and a comparative dispersion (sample D) using sample B.
(分散安定性評価)
試料C、D各40mlをプラスチックチューブに入れ、遠心分離機(himac CR21GII 日立工機社製)にて、5000rpmで1分間の遠心分級を行った。
遠心分級後の試料を目視で観察した結果、本発明の試料Cは試料Dに比べて、長期間の油性分散安定性に優れていることを確認した。
(Dispersion stability evaluation)
40 ml of each of Samples C and D was placed in a plastic tube, and centrifuged for 1 minute at 5000 rpm with a centrifuge (himac CR21GII manufactured by Hitachi Koki Co., Ltd.).
As a result of visual observation of the sample after centrifugal classification, it was confirmed that Sample C of the present invention was superior to Sample D in terms of long-term oil dispersion stability.
(紫外線遮蔽評価結果)
100ccのポリプロピレンカップに前記の分散体(試料C、D)それぞれ3gを入れ、シクロペンタシロキサン18.4gを加え、ホモミキサー(特殊機化工業社製、T.K.ROBOMICS)を用いて5000rpmで5分間分散した。この分散液をTACフィルム上に、膜厚25.4μmとなるようにアプリケーターで塗布し、分光光度計(日本分光株式会社製、V−660)を用いて275nmから750nmの波長で透過率を測定した。結果を表1に示す。本発明の分散体は、紫外線遮蔽能に優れており、可視光の透過率は同程度であることがわかった。
(Ultraviolet shielding evaluation results)
3 g of each of the above dispersions (samples C and D) is put into a 100 cc polypropylene cup, 18.4 g of cyclopentasiloxane is added, and the mixture is used at 5000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., TK ROBOMICS). Dispersed for 5 minutes. This dispersion was applied onto a TAC film with an applicator so as to have a film thickness of 25.4 μm, and the transmittance was measured at a wavelength of 275 nm to 750 nm using a spectrophotometer (manufactured by JASCO Corporation, V-660). did. The results are shown in Table 1. It was found that the dispersion of the present invention was excellent in ultraviolet shielding ability and had the same visible light transmittance.
本発明は、二層の加熱固定被覆を施した粉体であって、長期間の油性分散安定性、疎水安定性等に優れているため、化粧料、プラスチックの添加剤、インク、塗料、トナー(磁性粉、外添剤)、化学繊維、包装材料、電子材料等の各種分野で広く使用される。 The present invention is a powder having a heat-fixed coating of two layers, and is excellent in long-term oil dispersion stability, hydrophobic stability, etc., and therefore, cosmetics, plastic additives, inks, paints, and toners Widely used in various fields such as (magnetic powder, external additives), chemical fibers, packaging materials, electronic materials, etc.
Claims (5)
前記の工程で得られた粉体と第二被覆有機化合物とを気流粉砕機に入れ粉砕した後、不活性雰囲気下100〜200℃の温度で加熱処理して、その第一加熱固定被覆の上の少なくとも一部に第二加熱固定被覆を形成する工程とを含む、被覆粉体の製造方法。 The powder and the first coating organic compound are pulverized in an airflow pulverizer and then heat-treated at a temperature of 100 to 200 ° C. in an inert atmosphere to form a first heat-fixed coating on at least a part of the powder surface. And a process of
The powder obtained in the above step and the second coating organic compound are pulverized in an airflow pulverizer , and then heat-treated at a temperature of 100 to 200 ° C. in an inert atmosphere , so that the top of the first heat fixed coating is obtained. Forming a second heat-fixed coating on at least a part of the coating powder.
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JP7064902B2 (en) * | 2018-02-22 | 2022-05-11 | ベック株式会社 | Pigment dispersion and gloss adjustment method |
JP7639117B2 (en) | 2020-07-23 | 2025-03-04 | シャネル・パルファム・ボーテ | Surface-treated pigment and cosmetic composition containing the surface-treated pigment |
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JP5001486B2 (en) * | 2000-09-11 | 2012-08-15 | 三好化成株式会社 | Oil dispersion of powder having super-dispersion stability and cosmetics containing the same |
JP4317424B2 (en) * | 2003-10-31 | 2009-08-19 | 三好化成株式会社 | Oily dispersion of powder surface-treated with specific acidic ester oil, and cosmetic composition containing the same |
JP2005349305A (en) * | 2004-06-10 | 2005-12-22 | Kurimoto Ltd | Method of manufacturing mixed powder |
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